Ferroelectric Heterostructures Research Articles

Ultralow Strain-Induced Emergent Polarization Structures in a Flexible Freestanding BaTiO3 Membrane.

The engineering of ferroic orders, which involves the evolution of atomic structure and local ferroic configuration in the development of next-generation electronic devices. Until now, diverse polarization structures and topological domains are obtained in ferroelectric thin films or heterostructures, and the polarization switching and subsequent domain nucleation are found to be more conducive to building energy-efficient and multifunctional polarization structures. In this work, a continuous and periodic strain in a flexible freestanding BaTiO3 membrane to achieve a zigzag morphology is introduced. The polar head/tail boundaries and vortex/anti-vortex domains are constructed by a compressive strain as low as ≈0.5%, which is extremely lower than that used in epitaxial rigid ferroelectrics. Overall, this study c efficient polarization structures, which is of both theoretical value and practical significance for the development of next-generation flexible multifunctional devices.

Structural and Morphological Studies of Pt in the As-Grown and Encapsulated States and Dependency on Film Thickness.

The morphology and crystal structure of Pt films grown by pulsed laser deposition (PLD) on yttria-stabilized zirconia (YSZ)at high temperatures Tg = 900 °C was studied for four different film thicknesses varying between 10 and 70 nm. During the subsequent growth of the capping layer, the thermal stability of the Pt was strongly influenced by the Pt film's thickness. Furthermore, these later affected the film morphology, the crystal structure and hillocks size, and distribution during subsequent growth at Tg = 900 °C for a long duration. The modifications in the morphology as well as in the structure of the Pt film without a capping layer, named also as the as-grown and encapsulated layers in the bilayer system, were examined by a combination of microscopic and scattering methods. The increase in the thickness of the deposited Pt film brought three competitive phenomena into occurrence, such as 3D-2D morphological transition, dewetting, and hillock formation. The degree of coverage, film continuity, and the crystal quality of the Pt film were significantly improved by increasing the deposition time. An optimum Pt film thickness of 70 nm was found to be suitable for obtaining a hillock-free Pt bottom electrode which also withstood the dewetting phenomena revealed during the subsequent growth of capping layers. This achievement is crucial for the deposition of functional bottom electrodes in ferroelectric and multiferroic heterostructure systems.

Ferroelectric heterostructure nanocomposites based on Bi2MoO6 nanosheets and Bi2S3 nanorods for rapid piezocatalysis of organic dyes and antibiotics

Among numerous polluting compounds, the organic dyes and antibiotics are two servious factors causing water pollution. Hence, it is urgent to find a fast and safe way to degrade waste water in a sustainable approach. Here, ferroelectric heterostructure based on 2D Bi2MoO6 nanosheets and Bi2S3 nanorods has been prepared by a two-step solvothermal method for the reduction of organic dyes and antibiotics. Due to the energy band balance between Bi2S3 and Bi2MoO6, the formed type-II heterostructure can populate charge transfer at the junction and effectively inhibit electron-hole recombination. Under ultrasonic stimulation, catalytic active sites of a Bi2MoO6/Bi2S3 heterostructure for pollutant degradation can be generated through rapid charge transfer activation, thus enhancing the catalytic degradation effect of organic dyes and antibiotics. The Bi2MoO6/Bi2S3 heterostructure not only has good degradation effect, but also shows better stability. This work opens up new avenues for designing highly-efficient catalysts, which is of importance for wastewater degradation and energy-saving applications.

Optical Modulation of MoTe2/Ferroelectric Heterostructure via Interface Doping.

Optical modulation through interface doping offers a convenient and efficient way to control ferroelectric polarization, thereby advancing the utilization of ferroelectric heterostructures in nanoelectronic and optoelectronic devices. In this work, we fabricated heterostructures of MoTe2/BaTiO3/La0.7Sr0.3MnO3 (MoTe2/BTO/LSMO) and demonstrated opposite ultraviolet (UV) light-induced polarization switching behaviors depending on the varied thicknesses of MoTe2. The thickness-dependent band structure of MoTe2 film results in interface doping with opposite polarity in the respective heterostructures. The polarization field of BTO interacts with the interface charges, and an enhanced effective built-in field (Ebi) can trigger the transfer of massive UV light-induced carriers in both MoTe2 and BTO films. As a result, the interplay among the contact field of MoTe2/BTO, the polarization field, and the optically excited carriers determines the UV light-induced polarization switching behavior of the heterostructures. In addition, the electric transport characteristics of MoTe2/BTO/LSMO heterostructures reveal the interface barrier height and Ebi under opposite polarization states, as well as the presence of inherent in-gap trap states in MoTe2 and BTO films. These findings represent a further step toward achieving multifield modulation of the ferroelectric polarization and promote the potential applications in optoelectronic, logic, memory, and synaptic ferroelectric devices.

Improved Carrier Separation and Recombination by Ferroelectric Polarization in the CuBiP2Se6/C2N Heterostructure: A Nonadiabatic Molecular Dynamics Study.

The rapid recombination of photogenerated carriers heavily restricts the photocatalytic efficiency. Here, we propose a new strategy to improve catalytic efficiency based on the ferroelectric van der Waals heterostructure (CuBiP2Se6/C2N). Combining density functional theory and the nonadiabatic molecular dynamics (NAMD) method, we have systematically analyzed the ground-state properties and carrier dynamics images in the CuBiP2Se6/C2N heterostructure. Our calculations showed that the ferroelectric polarization of CuBiP2Se6 provides the internal driving force for the photogenerated carriers separation. NAMD results demonstrate that the excited-state carrier transfer and recombination processes in the CuBiP2Se6/C2N are consistent with a type II mechanism. Meanwhile, constructing the ferroelectric heterostructure can effectively prolong the carrier lifetime, from ∼65.98 to ∼124.54 ps. Moreover, the high quantum efficiency and tunable band edge positions mean that the CuBiP2Se6/C2N heterostructure is an excellent potential candidate material for photocatalytic water splitting.

Ferroelectric Control of Band Alignments in In2Se3/h‐BN and CuInP2S6/h‐BN van der Waals Heterostructures

Recently, 2D ferroelectric (FE) heterostructures have become a subject of great interest due to their potential device applications and the underlying physics involved. In this study, the first‐principles calculations are employed to examine the FE control of electronic structures in 2D FE heterostructures, specifically In2Se3/h‐BN and CuInP2S6 (CIPS)/h‐BN. In these results, it is demonstrated that by reversing the polarization of the FE layers, the band alignment of the heterostructures can be interconverted between type II and type I. For In2Se3/h‐BN, the variation of out‐of‐plane polarization can be attributed to the hindrance and facilitation of charge transfer from h‐BN to In2Se3 by the intrinsic electric field of the In2Se3 monolayer. For CIPS/h‐BN heterostructures, the higher transferred charge in the Cdn configuration due to the presence of built‐in electric fields and the stronger interfacial interaction in the Cdn configuration result in a higher polarization value compared to the Cdn configuration. Moreover, the carrier mobility of the heterostructures can also be effectively modulated by the FE polarization. In these findings, the potential significance of FE heterostructures with tunable band alignment and bandgap is highlighted in the development of nanoscale optoelectronic devices.

Electronic characteristics of the two-dimensional van der Waals ferroelectric α-In2Se3/Cs3Bi2I9 heterostructures

Two-dimensional (2D) van der Waals (vdWs) ferroelectric heterostructures provide a platform to design multifunctional electronic devices. In this Letter, the 2D vdWs ferroelectric α-In2Se3/Cs3Bi2I9 heterostructures were constructed to investigate the appropriate band alignment, effective masses, charge transfer, and polarization switching barriers by employing first-principle calculation. The results show that the polarization reversal of α-In2Se3 engineers band alignment transition from type-II (α-In2Se3-P↑/Cs3Bi2I9) to type-I (α-In2Se3-P↓/Cs3Bi2I9), resulting in an indirect bandgap changing from 0.09 to 0.75 eV. Calculated electron effective masses are isotropic, which is smaller than those of anisotropic hole effective masses. Interfacial charges transfer from Cs3Bi2I9 to α-In2Se3, which can be ascribed to work function difference. By combining non-equilibrium Green's functions, the current–voltage characteristics of α-In2Se3/Cs3Bi2I9 based ferroelectric tunnel junction were investigated, and the current on/off ratio of 103 is resulted by spatial charge carrier separation and recombination. The proposed electron–hole separation transport design strategy provides a comprehensive theoretical support for the development of microelectronic storage devices.

Programmable Ferroelectricity in Hf0.5Zr0.5O2 Enabled by Oxygen Defect Engineering.

Ferroelectricity, especially the Si-compatible type recently observed in hafnia-based materials, is technologically useful for modern memory and logic applications, but it is challenging to differentiate intrinsic ferroelectric polarization from the polar phase and oxygen vacancy. Here, we report electrically controllable ferroelectricity in a Hf0.5Zr0.5O2-based heterostructure with Sr-doped LaMnO3, a mixed ionic-electronic conductor, as an electrode. Electrically reversible extraction and insertion of an oxygen vacancy into Hf0.5Zr0.5O2 are macroscopically characterized and atomically imaged in situ. Utilizing this reversible process, we achieved multilevel polarization states modulated by the electric field. Our study demonstrates the usefulness of the mixed conductor to repair, create, manipulate, and utilize advanced ferroelectric functionality. Furthermore, the programmed ferroelectric heterostructures with Si-compatible doped hafnia are desirable for the development of future ferroelectric electronics.

Effects of interfacial buffering layer on imprint and domain switching dynamics in Pb(Zr,Ti)O3 thin-film heterostructures

Interfacial engineering is important for ferroelectric thin-film heterostructures because of the modulation of boundary conditions of the spontaneous polarizations and their switching behaviors, which are essential for ferroelectric electronics. In this work, we study the effects of interfacial buffering layer, 5-nm-thick SrTiO3 (STO), on the imprint and domain switching of epitaxial Pt/Pb(Zr,Ti)O3/SrRuO3 (SRO) thin-film heterostructures and capacitors. By buffering the ultrathin SrTiO3 layer at the Pb(Zr,Ti)O3 surface, the imprint effect can be dramatically alleviated as observed in the piezoresponse force microscopy (PFM)-measured domain structures and polarization–electric field hysteresis loops in thin-film capacitors. However, when the SrTiO3 layer is buffered at the Pb(Zr,Ti)O3/SrRuO3 interface, the imprint effect is slightly increased. These phenomena are explained based on the band alignments among the Pt and SrRuO3 electrodes and the Pb(Zr,Ti)O3 layer associated with the existence of oxygen vacancies in the SrTiO3 layer. With the reduction of imprint effect, the domain switching dynamics are also improved in the SrTiO3-buffered Pb(Zr,Ti)O3 capacitor, in which the switching activation field is decreased by about 45.3% in comparison with that of the pristine capacitor. These results facilitate the design and optimization of ferroelectric devices with the improvements in domain configurations, switching behaviors and band alignments.

Nonvolatile electric-field control of topological phase transition in a two-dimensional ferroelectric heterostructure

Topological phase transitions can be controlled by nonvolatile electric-fields through ferroelectric heterostructure engineering.

(Invited) Ferroelectric Nitride Semiconductors: Epitaxy, Properties, and Emerging Device Applications

The incorporation of rare-earth elements such as scandium (Sc) can transform conventional III-nitride semiconductors to be ferroelectric. In this talk I will present recent advances of ferroelectric Sc-III-nitride heterostructures and nanostructures, including epitaxy, properties and emerging device applications. Molecular beam epitaxy and properties of ScAlN and ScGaN with a wide range of Sc compositions will be discussed. Special attention will be paid to the unique ferroelectric properties of these ultrawide bandgap semiconductors. The realization of ultrathin ferroelectric nitride heterostructures and the underlying physics and properties will be discussed, together with their applications in quantum photonics and electronics.

Volume-Confined Fabrication of Large-Scale Single-Crystalline Molecular Ferroelectric Thin Films and Their Applications in 2D Materials.

With outstanding advantages of chemical synthesis, structural diversity, and mechanical flexibility, molecular ferroelectrics have attracted increasing attention, demonstrating themselves as promising candidates for next-generation wearable electronics and flexible devices in the film form. However, it remains a challenge to grow high-quality thin films of molecular ferroelectrics. To address the above issue, a volume-confined method is utilized to achieve ultrasmooth single-crystal molecular ferroelectric thin films at the sub-centimeter scale, with the thickness controlled in the range of 100-1000nm. More importantly, the preparation method is applicable to most molecular ferroelectrics and has no dependency on substrates, showing excellent reproducibility and universality. To demonstrate the application potential, two-dimensional (2D) transitional metal dichalcogenide semiconductor/molecular ferroelectric heterostructures are prepared and investigated by optical spectroscopic method, proving the possibility of integrating molecular ferroelectrics with 2D layered materials. These results may unlock the potential for preparing and developing high-performance devices based on molecular ferroelectric thin films.

Controllable Electrocatalytic to Photocatalytic Conversion in Ferroelectric Heterostructures.

Photocatalytic and electrocatalytic reactions to produce value-added chemicals offer promising solutions for addressing the energy crisis and environmental pollution. Photocatalysis is driven by light excitation and charge separation and relies on semiconducting catalysts, while electrocatalysis is driven by external electric current and is mostly based on metallic catalysts with high electrical conductivity. Due to the distinct reaction mechanism, the conversion between the two catalytic types has remained largely unexplored. Herein, by means of density functional theory (DFT) simulations, we demonstrated that the ferroelectric heterostructures Mo-BN@In2Se3 and WSe2@In2Se3 can exhibit semiconducting or metallic features depending on the polarization direction as a result of the built-in field and electron transfer. Using the nitrogen reduction reaction (NRR) and hydrogen evolution reaction (HER) as examples, the metallic heterostructures act as excellent electrocatalysts for these reactions, while the semiconducting heterostructures serve as the corresponding photocatalysts with improved optical absorption, enhanced charge separation, and low Gibbs free energy change. The findings not only bridge physical phenomena of the electronic phase transition with chemical reactions but also offer a new and feasible approach to significantly improve the catalytic efficiency.

A Flexible Magnetic Field Sensor Based on PZT/CFO Bilayer via van der Waals Oxide Heteroepitaxy.

Magnetoelectric (ME) magnetic field sensors utilize ME effects in ferroelectric ferromagnetic layered heterostructures to convert magnetic signals into electrical signals. However, the substrate clamping effect greatly limits the design and fabrication of ME composites with high ME coefficients. To reduce the clamping effect and improve the ME response, a flexible ME sensor based on PbZr0.2Ti0.8O3 (PZT)/CoFe2O4 (CFO) ME bilayered heterostructure was deposited on mica substrates via van der Waals oxide heteroepitaxy. A saturated magnetization of 114.5 emu/cm3 was observed in the bilayers. The flexible sensor exhibited a strong ME coefficient of 6.12 V/cm·Oe. The local ME coupling has been confirmed by the evolution of the ferroelectric domain under applied magnetic fields. The flexible ME sensor possessed a stable response with high sensitivity to both AC and DC weak magnetic fields. A high linearity of 0.9988 and sensitivity of 72.65 mV/Oe of the ME sensor were obtained under flat states. The ME output and limit-of-detection under different bending states showed an inferior trend as the bending radius increased. A flexible proximity sensor has been demonstrated, indicating a promising avenue for wearable device applications and significantly broadening the potential application of the flexible ME magnetic field sensors.

Two-dimensional ferroelectric heterostructures for overall water-splitting from DFT aspects

Currently, the construction of direct Z-type heterojunctions is an effective way to improve the overall water splitting catalytic efficiency of existing two-dimensional(2D) materials, which can simultaneously combine spatial separation of active sites and enhanced redox ability. In particular, when the internal structure of heterojunction was polarized, the polarization can effectively tune electronic properties and remove band gap (1.23 eV) limitation on water splitting. So far, the effect of polarization on water-splitting reactivity in heterojunctions based on the 2D layered polarized In2Y3 (Y = S, Se) and the nonpolarized 2D β-Sb monolayer is unclear. Therefore, we constructed a series of such heterojunctions and made theoretical predictions of overall water splitting performance by first-principles calculations. The predictions shown that As/In2Se3(up), Sb/In2Se3(down) and Sb/In2S3(down) are potential photocatalysts with direct Z-scheme band positions, and hydrogen evolution reaction (HER) and oxygen evolution reaction (OER) will occur on different surfaces of system. It is found that the intrinsic polarization electric field of In2Y3 (Y = S, Se) monolayer effectively enhances photogenerated carrier driving force of reaction. Notably, the promising photocatalysts have a high solar-hydrogen (STH) efficiency of 17.71 %, which has potential commercial applications. Also, Bi/In2S3up (S) and As/In2Te3up (As) exhibit desirable electrocatalytic HER performance. These insights provide an important strategy for application of ferroelectric heterojunctions in water splitting.

Ferroelectric polarization reversals in C2N/α-In2Se3 van der Waals heterostructures: a conversion from the traditional type-II to S-scheme.

Introduction: Ferroelectric substances, characterized by inherent spontaneous polarization, can boost photocatalytic efficiency by facilitating the separation of photogenerated carriers. However, conventional photocatalysts with perovskite-class ferroelectricity are generally constrained by their 3D arrangement, leading to less accessible active sites for catalysis and a smaller specific surface area compared to a 2D layout. Methods: In my research, I developed a 2D ferroelectric heterostructure consisting of C2N/α-In2Se3. I performed first-principle calculations on the 2D C2N/α-In2Se3 heterostructure, specifically varying the out-of-plane ferroelectric polarization directions. I primarily focused on C2N/α-In2Se3 (I) and C2N/α-In2Se3 (II) heterostructures. Results: My findings revealed that reversing the ferroelectric polarization of the 2D α-In2Se3 layer in the heterostructures led to a transition from the conventional type-II [C2N/α-In2Se3 (I)] to an S-scheme [C2N/α-In2Se3 (II)]. The S-scheme heterostructure [C2N/α-In2Se3 (II)] demonstrated a high optical absorption rate of 17% in visible light, marking it as a promising photocatalytic material. Discussion: This research underscores the significance of ferroelectric polarization in facilitating charge transfer within heterogeneous structures. It provides a theoretical perspective for developing enhanced S-scheme photocatalysts, highlighting the potential of 2D ferroelectric heterostructures in photocatalytic applications.

Electrically modulated photoresponse and optically modulated electroresistance in a ferroelectric heterostructure with PbZr0.2Ti0.8O3 barriers

Ferroelectric heterostructures hold great promise for developing multifunctional memristors and optoelectronic devices. In this study, we report a ferroelectrically modulated photoresponse and optically modulated electroresistance behaviors in the Pt/PbZr0.2Ti0.8O3(PZT)/Nb-doped SrTiO3 (NSTO) heterostructure. The short-circuit photocurrent rises from 28 nA (after poling at +5 V) to 345 nA (after poling at −5 V) when illuminated with 360 nm of 10 mW·cm−2, exhibiting a massive photocurrent variation ratio of 1230%. This result can be attributed to the modulation of the ferroelectric polarization on the built-in field at the PZT/NSTO interface, which impacts the separation of photogenerated carriers. Furthermore, the heterostructure has a large high/low resistance ratio of 6 × 105%, which decreases to 2 × 104% when illuminated with 360 nm light. This finding is attributed to ferroelectric polarization and light illumination modulating the barrier height and width. Overall, this research suggests a promising strategy for developing self-powered heterojunction photodetectors and multifunctional memory devices.

Phase field study on the flexoelectric response of dielectric–ferroelectric multilayers

We report a theoretical modeling of the flexoelectric response of dielectric–ferroelectric (DE–FE) multilayers based on phase field simulations in the framework of the Landau–Ginzburg–Devonshire (LGD) theory. The correlation between negative capacitance and flexoelectric response is revealed, and the single-domain and multi-domain models are compared. It shows that the dielectric layers drive the ferroelectric layer into a negative capacitance regime, and the flexoelectric response of the multilayer is maximal when the negative capacitance of the ferroelectric layer has a minimal absolute value. Moreover, the flexoelectric response peak will be shifted to a lower temperature by increasing the thickness of dielectric layer, indicating a possibility of achieving a stronger flexoelectric response at room temperature compared with that of pure ferroelectric. However, while the single-domain model shows that the flexoelectric response peak is simply shifted to a lower temperature with near constant peak value and width, the multi-domain model reveals a significant suppressing of the flexoelectric peak by the dielectric layer. This is attributed to the formation of the vortex domain state, which eases the depolarization effect and leads to large absolute value of negative capacitance of the ferroelectric layer. Our work provides new insights into flexoelectricity in ferroelectric heterostructures.

Schottky Barrier Control of Self-Polarization for a Colossal Ferroelectric Resistive Switching.

Controlling the domain evolution is critical both for optimizing ferroelectric properties and for designing functional electronic devices. Here we report an approach of using the Schottky barrier formed at the metal/ferroelectric interface to tailor the self-polarization states of a model ferroelectric thin film heterostructure system SrRuO3/(Bi,Sm)FeO3. Upon complementary investigations of the piezoresponse force microscopy, electric transport measurements, X-ray photoelectron/absorption spectra, and theoretical studies, we demonstrate that Sm doping changes the concentration and spatial distribution of oxygen vacancies with the tunable host Fermi level which modulates the SrRuO3/(Bi,Sm)FeO3 Schottky barrier and the depolarization field, leading to the evolution of the system from a single domain of downward polarization to polydomain states. Accompanied by such modulation on self-polarization, we further tailor the symmetry of the resistive switching behaviors and achieve a colossal on/off ratio of ∼1.1 × 106 in the corresponding SrRuO3/BiFeO3/Pt ferroelectric diodes (FDs). In addition, the present FD also exhibits a fast operation speed of ∼30 ns with a potential for sub-nanosecond and an ultralow writing current density of ∼132 A/cm2. Our studies provide a way for engineering self-polarization and reveal its strong link to the device performance, facilitating FDs as a competitive memristor candidate used for neuromorphic computing.

The reversible and nonvolatile properties of 2D LaBr2/α-In2Se3 heterostructure by strain and electric field modulation

Two-dimensional (2D) ferroelectric materials have intrinsic polarized electric field, when they stack with other 2D materials to construct ferroelectric van der Waals heterostructures, they will produce a lot of novel properties, which has aroused extensive research interests. Therefore, based on first-principle calculations, we have comprehensively studied the electronic properties of LaBr2/α-In2Se3 ferroelectric heterostructures to investigate the reversibility and nonvolatility with information. Our calculations show that, the system is a ferromagnetic semiconductor with intrinsic valley polarization when α-In2Se3 is in the ferroelectric polarized up state. By switching the ferroelectric polarization of α-In2Se3, the heterostructure undergoes a transition from semiconductor to half metal, which can be attributed to the competition between the built-in electric field (Eint) and the polarized electric field Epi→,generated by the charge transfer at interface of heterostructure and the bound charge of α-In2Se3, respectively. Besides, the band arrangement types of LaBr2/α-In2Se3 heterostructure can be well modulated under extra electric filed and biaxial strain. Furthermore, we have observed valley-submerging under electric filed and strain, which indicates the valleytronic nature can also be on-off in LaBr2/α-In2Se3 heterostructures. More importantly, the realization of reversible and non-volatile properties depends on the intrinsic characteristics of heterostructure and does not require external mechanisms. Our research not only provides the possibility for the application of the LaBr2/α-In2Se3 heterostructures in nanodevices, but also give the theoretical support to the study of spintronics and valleytronics.